Abstract: | The development of efficient methods for stereocontrolled synthesis of polyol derivatives has been of continuing interest for the synthetic community. We describe herein tandem olefin cross‐metathesis/hemiacetalization/intramolecular oxa‐Michael addition of allylic/homoallylic alcohols, α,β‐unsaturated ketones, and aldehydes, which enabled the synthesis of syn‐1,2‐ and syn‐1,3‐diol derivatives in a step‐economical manner. A series of differentially protected polyol derivatives could be obtained in subsequent transformations via chemoselective/regioselective cleavage of the acetal moiety of the tandem reaction products. |